The present invention relates to nonoxidative colorants for keratin fibers, for example hair or wool, based on a combination of natural or synthetic nonoxidative dyes (known as xe2x80x9cdirect dyesxe2x80x9d) and polymethine dyes, as well as to a method for coloring keratin fibers.
The coloring of hair is currently subject to the most varied trends. Whereas in the past hair was colored primarily to cover gray areas, today there is an increasing demand for integrating the hair color into current fashion as an expression of personality.
Now as before, two established methods of hair coloring are available. One of these is the oxidative hair coloring which results in very durable tints. The other method consists of the possibility of coloring hair with colorants containing nonoxidative, direct dyes (often referred to as toners). Although the dyes used for this purpose are optimized for dyeing performance as well as for remaining on the hair as long as possible, the color shade gradually weakens with every hair washing. Thus, as a rule and depending on the product used and the type of hair, such colorants do not last more than a maximum of 10 hair washings.
Hence, a need exists for nonoxidative colorants which besides good coloring properties have improved color stability, particularly in terms of wash-out resistance.
Surprisingly, we have now found that colorants based on a combination of natural or synthetic nonoxidative dyes and polymethine dyes (in the following also referred to as xe2x80x9coxonol dyesxe2x80x9d) produce an outstanding and, in particular, very long-lasting coloring of keratin fibers.
Oxonol dyes have been known for a long time, and a wide range of substitution patterns can be found in the literature. A review of these dyes can be found, for example, in Houben-Weyl 5/1d, 4th edition (1954), page 227 ff. Some of these oxonol dyes are also available commercially.
By means of the colorants of the invention, it is possible to achieve color shades of a modified natural tone, but particularly those in the fashionable range. Moreover, besides the said color shades, it is possible to obtain a number of vivid color highlights, particularly in the bright-red to blue range. As a result of the high tinting power of the dyes and their high substantivity, the original fiber color can be covered very effectively. As a result, it is possible to satisfy the aforementioned desire to integrate the hair color into fashion and to provide an expression of personality.
The object of the present application is therefore a colorant for keratin fibers, for example furs, feathers, wool and hair, particularly human hair, characterized in that it contains a combination of (a) at least one natural or synthetic nonoxidative dye and (b) at least one polymethine dye having the tautomeric formula (Ia)(Ib) or a physiologically tolerated salt thereof 
wherein in general formula (Ia)(Ib) X and Y independently of each other and together with the two carbon atoms of the ring system indicated in formula (Ia)(Ib) represent the elements needed for the formation of a five-membered or six-membered heterocyclic ring, and L stands for a linking group of general formula 
wherein R denotes a hydrogen atom, a phenyl, methyl or carboxamido group or a halogen atom, and indices m and n are equal to 0, 1 or 2, the sum of m and not exceeding 2.
For example, the five-membered or six-membered heterocyclic ring in general formula (Ia)(Ib) can be a pyrazolone, pyridone, isoxazolone, dioxothiazoline, rhodanine, dioxoimidazolidine, barbituric acid or thiobarbituric acid group, the two ring systems present in general formula (Ia)(Ib) being equal or different. Preferably, taking into account their tautomeric forms, these two ring systems are identical, and L stands for a monomethine, trimethine or pentamethine unit.
Suitable physiologically tolerated salts of the compounds of formula (Ia)(Ib) are, in particular, the alkali metal and ammonium salts, for example the ammonium, triethylammonium, sodium, potassium, N-methylmorpholinium, monoethanolammonium, diethanolammonium and triethanolammonium salts among which the sodium, potassium and particularly the ammonium salts are preferred.
Written in their acid form, the dyes of formula (I) used in the colorant of the invention contain polymethine dyes of general formulas (II) to (IV), presented in their possible tautomeric forms 
wherein R1, R1xe2x80x2 and R6 denote hydrogen, a straight-chain or branched C1 to C8 alkyl, hydroxyethyl, dihydroxypropyl, methoxyethyl, carboxyethyl or C1 to C4 sulfoalkyl group, a phenyl radical, a phenyl radical substituted with one or more halogen atoms, a phenyl radical substituted with one or two sulfonic acid groups, a phenyl radical substituted with one or two carboxylic acid groups, a phenyl radical substituted with one or more unbranched or branched C1 to C8 alkyl groups or C1 to C8 alkoxy groups, a benzyl radical, a benzyl radical substituted with one or more halogen atoms, a benzyl radical substituted with a C1 to C4 alkyl, a hydroxyl, methoxy, carboxyl, nitro or amino group or a five-membered or six-membered saturated or unsaturated heterocyclic ring, R1 and R1xe2x80x2 being equal or different;
R2, R2xe2x80x2 and R7 denote hydrogen, a branched or unbranched C1 to C6 alkyl group, a phenyl radical, an amino group which can also be acylated or sulfonylated, an acetyl or methoxy or a carboxylic acid group esterified with a straight-chain or branched C1 to C8 alcohol or ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, or a carboxamido, carboxanilido or 2-amino-2-oxyethyl or nitrile group, R2 and R2xe2x80x2 being equal or different; and
R3, R3xe2x80x2 and R8 denote hydrogen, a straight-chain or branched C1 to C11 alkyl group, a monohydroxyalkyl group, a straight-chain or branched C1 to C11 dihydroxyalkyl group, a straight-chain or branched C1 to C11 alkoxyalkyl group, a straight-chain or branched C1 to C11 monoalkylamino group, an amino group having formula (CH2)xxe2x80x94NR11R12 (wherein x stands for an integer from 0 to 3 and R11 and R12 independently of each other denote a C1 to C3 alkyl group), a C2 to C4 sulfoalkyl or carboxyalkyl group, a phenyl group or a phenyl group substituted with one or more halogen atoms, or a phenyl group substituted with one or two sulfonic acid groups, or with one or two carboxyl groups, or with one or more unbranched or branched C1 to C8 alkyl groups or with C1 to C8 alkoxy groups, or a benzyl group or a benzyl group substituted with one or more halogen atoms, or with a C1 to C4 alkyl, hydroxyl, methoxy, nitro or amino group, or a phenylethyl group, a five-membered or six-membered aromatic or nonaromatic heterocyclic ring which can be linked directly through a methylene group, a pyrolidino, morpholino, piperazino, piperidino or pyridino (C2 or C3) alkyl group or a trialkylammonium group of formula R13xe2x80x94N(R14)3+ (wherein R13 denotes a C1 to C6 alkylene group and R14 denotes a methyl or ethyl group, the total number of carbon atoms in the molecule being 5 to 9), R3 and R3xe2x80x2 being equal or different, and
R4, R4xe2x80x2 and R9 denote hydrogen, a nitrile, carboxylate ester, carboxamido, sulfonic acid, sulfomethyl or methanesulfonyl group or a pyridinium or imidazolium radical, R4 and R4xe2x80x2 being equal or different, and
R5, R5xe2x80x2 and R10 denote hydrogen or a C1 to C4 alkyl group or a C5-C6 cycloalkyl, phenylethyl, methoxyphenyl, benzyl, phenyl or carboxyl group, R5 and R5xe2x80x2 being equal or different, and
Z denotes oxygen or a radical of formula C(CN)2, C(CN)COOQ or C(COOQ)2 wherein Q denotes a C1 to C8 alkyl group or an ethylene glycol mono-(C3 to C7)-alkyl ether, and L denotes a linking group of general formula 
xe2x80x83wherein R denotes a hydrogen atom, a phenyl, methyl or carboxamido group or a halogen atom, and the indices m and n equal 0, 1 or 2, the sum of m and n not exceeding 2.
Particularly preferred are dyes of general formulas (II) to (IV) and the salts thereof wherein
R1 and R1xe2x80x2 are equal and denote hydrogen, a straight-chain or branched C1 to C4 alkyl group, a hydroxyethyl, dihydroxypropyl, methoxyethyl or C2 to C4 sulfoalkyl group, a phenyl radical or a phenyl radical substituted with one or more halogen atoms, one or two sulfonic acid groups, a methyl or methoxy group, or a benzyl radical or a benzyl radical substituted with a halogen atom, a methyl, hydroxyl, methoxy, nitro or amino group, and
R2 and R2xe2x80x2 are equal and denote a methyl group or an amino group which can also be acylated, or a carboxyl group possibly esterified with a C1 to C3 alcohol, and R3 and R3xe2x80x2 are equal or different and denote hydrogen, a straight-chain C1 to C4 alkyl group, a hydroxyethyl, methoxyethyl, methoxypropyl or sulfoethyl group or a phenyl radical or a phenyl radical substituted with a halogen atom, a sulfonic acid or methyl or methoxy group, or a benzyl radical or a benzyl radical substituted with a halogen atom, a methyl, hydroxyl, methoxy, nitro or amino group or a five-membered or six-membered aromatic or nonaromatic heterocyclic ring which can be linked directly or through a methylene group; an amino group, a C1 to C4 monoalkylamino group or a dialkylamino group with a total of 2 to 8 carbon atoms in the molecule, or a trialkylammoniumalkyl group of formula R13xe2x80x94N(R14)3+ (wherein R13 denotes a C1 to C6 alkylene group and R14 denotes a methyl or ethyl group, the total number of carbon atoms in the molecule being equal to 5 to 9), and
R4 and R4xe2x80x2 are equal and denote hydrogen, a nitrile, carboxamido, sulfonic acid, sulfomethyl, methanesulfonyl, pyridinium, or imidazolium group, and
R5 and R5xe2x80x2 are equal and denote hydrogen, a methyl or nitrile group or a substituted or unsubstituted phenyl radical, and
R6 denotes hydrogen, a straight-chain or branched C1 to C4 alkyl group or a hydroxyethyl, dihydroxypropyl, methoxyethyl or C2 to C4 sulfoalkyl group or a phenyl radical or a phenyl radical substituted with one or more halogen atoms, one or two sulfonic acid groups, a methyl or methoxy group; a benzyl radical or a benzyl radical substituted with a halogen atom, or a methyl, hydroxyl, methoxy, nitro or amino group, and
R7 denotes a methyl group or an amino group which can also be acylated, a carboxyl group or a carboxyl group esterified with a C1 to C3 alcohol, and
R8 denotes hydrogen, a straight-chain C1 to C4 alkyl group, a hydroxyethyl, methoxyethyl or sulfoethyl group, a phenyl radical or a phenyl radical substituted with a halogen atom, sulfonic acid, methyl or methoxy group; a benzyl radical or a benzyl radical substituted with a halogen atom or a methyl, hydroxyl, methoxy, nitro or amino group; or a five-membered or six-membered aromatic or nonaromatic heterocyclic ring linked directly or through a methylene group, an amino or C1 to C4 monoalkylamino group, a dialkylamino group with a total of 2 to 8 carbon atoms in the molecule or a trialkylammoniumalkyl group R13xe2x80x94N(R14)3+ (wherein R13 denotes a C1 to C6 alkylene group and R14 denotes a methyl or ethyl group, the total number of carbon atoms in the molecule being 5 to 9), and
R9 denotes hydrogen, a nitrile, carboxamido, sulfonic acid, sulfomethyl, pyridinium or imidazolium group, and
R10 denotes hydrogen, a methyl or nitrile group or a substituted or unsubstituted phenyl radical, and
Z denotes oxygen or a C(CN)2 group, and
L is a linking group of general formula 
xe2x80x83wherein R stands for a hydrogen atom or a methyl group, and the indices m and n are equal to 0, 1 or 2, the sum of m and n not exceeding 2.
The compounds shown in the following (in one of their possible tautomeric forms) are examples of the aforesaid preferred dyes of formulas (II) to (IV). Written in their acid form, they are as follows. 
4-(5-Hydroxy-1,3-dimethyl-1H-pyrazol-4-ylmethylen)-2,5-dimethyl-2,4-dihydropyrazol-3-one (1) 
2-(2-Hydroxyethyl)4-(5-hydroxy-1-(2-hydroxyethyl)-3-methyl-1H-pyrazol-4-ylmethylen)-5-methyl-2,4-dihydropyrazol-3-one (2) 
4-(5-Hydroxy-3-methyl-1-(4-sulfophenyl)-1H-pyrazol-4-ylmethylen)-5-methyl-2-(4-sulfophenyl)-2,4-dihydropyrazol-3-one (3) 
4-(3-(5-Hydroxy-1,3-dimethyl-1H-pyrazol4-yl)-allyliden)-2,5-dimethyl-2,4-dihydropyrazol-3-one (4) 
5-Amino-4-(3-(3-amino-5-hydroxy-1-phenyl-1H-pyrazol-4-yl)-allyliden)-2-phenyl-2,4-dihydropyrazol-3-one (5) 
2-(2-Hydroxyethyl)-4-(3-(5-hydroxy-1-(2-hydroxyethyl)-3-methyl-1H-pyrazol-4-yl)-allyliden)-5-methyl-2,4-dihydro-pyrazol-3-one (6) 
4-(3-(5-Hydroxy-3-methyl-1-(4-sulfophenyl)-1H-pyrazol-4-yl)-allyliden)-5-methyl-2-(4-sulfophenyl)-2,4-dihydro-pyrazol-3-one (7) 
4-(3-(5-Hydroxy-3-methyl-1-(4-sulfophenyl)-1H-pyrazol-4-yl)-but-2-enyliden)-5-methyl-2-(4-sulfophenyl)-2,4-dihydropyrazol-3-one (8) 
4-(3-(3-Carboxy-5-oxo-1-(4-sulfophenyl)-1,5-dihydropyrazol-4-yliden)-propenyl)-5-hydroxy-1-(4-sulfophenyl)-1H-pyrazol-3-carboxylic acid (9) 
5-Hydroxy4-(3-(3-methoxycarbonyl-5-oxo-1-(4-sulfophenyl)-1,5-dihydropyrazol-4-yliden)-propenyl)-1-(4-sulfophenyl)-1H-pyrazol-3-carboxylic acid methyl ester (10) 
4-(5-(5-Hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)-penta-2,4-dienyliden)-2,5-dimethyl-2,4-dihydropyrazol-3-one (11) 
5-Amino-4-(5-(3-amino-5-hydroxy-1-phenyl-1H-pyrazol-4-yl)-penta-2,4-dienyliden)-2-phenyl-2,4-dihydropyrazol-3-one (12) 
2-(2-Hydroxyethyl)-4-(5-(5-hydroxy-1-(2-hydroxyethyl)-3-methyl-1H-pyrazol-4-yl)-penta-2,4-dienyliden)-5-methyl-2,4-dihydro-pyrazol-3-one (13) 
4-(5-(5-Hydroxy-3-methyl-1-(4-sulfophenyl)-1H-pyrazol-4-yl)-penta-2,4-dienyliden)-5-methyl-2-(4-sulfophenyl)-2,4-dihydropyrazol-3-one (14) 
4-(5-(3-Carboxy-5-oxo-1-(4-sulfophenyl)-1,5-dihydropyrazol-4-yliden)-penta-1,3-dienyl)-5-hydroxy-1-(4-sulfophenyl)-1H-pyrazol-3-carboxylic acid (15) 
6-Hydroxy-1-(2-hydroxyethyl)-5-(3-(1-(2-hydroxyethyl)-3-methyl-5-oxo-1,5-dihydro-pyrazol-4-yliden)-propenyl)-4-methyl-2-oxo-1,2-dihydro-pyridin-3-carbonitrile (16) 
6-Hydroxy-5-(3-(1-(2-hydroxyethyl)-3-methyl-5-oxo-1,5-dihydro-pyrazol-4-yliden)-propenyl)-4-methyl-2-oxo-1-(4-sulfophenyl)-1,2-dihydro-pyridin-3-carbonitrile (17) 
6-Hydroxy-4-methyl-5-(3-(3-methyl-5-oxo-1-(4-sulfophenyl)-1,5-dihydropyrazol-4-yliden)-propenyl)-2-oxo-1-(4-sulfophenyl)-1,2-dihydropyridin-3-carbonitrile (18) 
6-Hydroxy-4-methyl-5-(3-(3-methyl-5-oxo-1-phenyl-1,5-dihydropyrazol-4-yliden)-propenyl)-2-oxo-1-(3-sulfophenyl)-1,2-dihydropyridin-3-carbonitrile (19) 
4-(3-(5-Cyano-2-hydroxy4-methyl-6-oxo-1-phenyl-1,6-dihydropyridin-3-yl)-allyliden)-5-oxo-1-(4-sulfophenyl)-4,5-dihydro-1H-pyrazol-3-carboxylic acid (20) 
6-Hydroxy-5-(3-(1-(2-hydroxyethyl)-3-methyl-5-oxo-1,5-dihydropyrazol-4-yliden)-propenyl)-4-methyl-2-oxo-1-phenyl-1,2-dihydropyridin-3-carbonitrile (21) 
5-(3-(4-Carboxy-2,6-dioxo-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-6-hydroxy-2-oxo-1,2-dihydropyridin-4carboxylic acid (22) 
2-(3-Cyano-5-(3-(5-cyano-6-dicyanomethylen-4-methyl-2-oxo-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-6-hydroxy-4-methyl-1H-pyridin-2-yliden)-malononitrile (23) 
5-(3-(5-Cyano-1-ethyl-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-1-ethyl-6-hydroxy-4-methyl-2-oxo-1 ,2-dihydropyridin-3-carbonitrile (24) 
5-(3-(5-Cyano-1-(2-hydroxyethyl)-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-6-hydroxy-1-(2-hydroxyethyl)-4-methyl-2-oxo-1,2-dihydropyridin-3-carbonitrile (25) 
5-(3-(5-Cyano-1-ethyl-4-(4-methoxyphenyl)-2,6-dioxo-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-1-ethyl-6-hydroxy-4-(4-methoxyphenyl)-2-oxo-1,2-dihydropyridin-3-carbonitrile (26) 
1-Butyl-5-(3-(1-butyl-5-cyano-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridin-3-carbonitrile (27) 
5-(3-(5-Cyano-1-(3-methoxy-propyl)4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-6-hydroxy-1-(3-methoxy-propyl)-4-methyl-2-oxo-1,2-dihydropyridin-3-carbonitrile (28) 
5-(3-(5-Cyano-1-cyclohexyl-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridin-3-carbonitrile (29) 
5-(3-(5-Cyano-4-methyl-1-(2-morpholin-4-yl-ethyl)-2,6-dioxo-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-6-hydroxy-4-methyl-1-(2-morpholin-4-yl-ethyl)-2-oxo-1,2-dihydropyridin-3-carbonitrile (30) 
5-(3-(5-Cyano-4-methyl-2,6-dioxo-1-(4-sulfophenyl)-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-6-hydroxy-4-methyl-2-oxo-1-(4-sulfophenyl)-1,2-dihydropyridin-3-carbonitrile (31) 
5-(3-(5-Cyano-4-methyl-2,6-dioxo-1-(3-sulfophenyl)-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-6-hydroxy-4-methyl-2-oxo-1-(3-sulfophenyl)-1,2-dihydropyridin-3-carbonitrile (32) 
5-(3-(5-Cyano-1-dimethylamino-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-1-dimethylamino-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridin-3-carbonitrile (33) 
5-(3-(5-Carbamoyl-1-ethyl-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridin-3-carboxamide (34) 
1-Ethyl-3-(3-(1-ethyl-2-hydroxy-5-methansulfonyl-4-methyl-6-oxo-1,6-dihydro-pyridin-3-yl)-allyliden)-5-methansulfonyl-4-methyl-3H-pyridin-2,6-dione (35) 
5-(5-(5-Cyano-1-ethyl-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-yliden)-penta-1,3-dienyl)-1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridin-3-carbonitrile (36)
Preferred among the aforesaid dyes are, in particular the compounds of formula (II) to (IV) wherein
R1 and R1xe2x80x2 are equal and denote a phenyl, sulfophenyl, methyl or hydroxyethyl group,
R2 and R2xe2x80x2 are equal and denote hydrogen, a methyl, carboxyl, carboxylate ester or amino group,
R3 and R3xe2x80x2 independently of each other denote hydrogen or a straight-chain C1 to C4 alkyl group, a methoxy, hydroxyethyl, sulfoethyl, phenyl or sulfophenyl group,
R4 and R4xe2x80x2 are equal and denote hydrogen, or a nitrile or carboxamido group,
R6 denotes a phenyl, sulfophenyl, methyl or hydroxyethyl group,
R7 denotes hydrogen, or a methyl, carboxyl, carboxylate ester or amino group,
R8 denotes hydrogen or a straight-chain C1 to C4 alkyl group, a methoxyethyl, hydroxyethyl, sulfoethyl, phenyl or sulfophenyl group,
R9 denotes a nitrile group,
R10 denotes a methyl or carboxyl group,
Z denotes oxygen,
R denotes a hydrogen atom or a methyl group, and the indices m and n equal 0, 1 or 2, the sum of m and n having a maximum value of 2.
In the case of dyes with a pronounced anionogenic character (this is true primarily for dyes containing acid functions such as sulfonic acid or carboxyl groups), the dyes can be used also in the form of their physiologically tolerated salts. Suitable, in particular, are the following compounds. 
Diammonium-4-(5-hydroxy-3-methyl-1-(4-sulfophenyl)-1H-pyrazol-4-yl-methylen)-5-methyl-2-(4-sulfophenyl)-2,4-dihydro-pyrazol-3-one (3a) 
Disodium 4-(3-(5-hydroxy-3-methyl-1-(4-sulfophenyl)-1H-pyrazol-4-yl)-allyliden)-5-methyl-2-(4-sulfophenyl)-2,4-dihydro-pyrazol-3-one (7a) 
Tripotassium 4-(3-(5-hydroxy-3-methyl-1-(4-sulfophenyl)-1H-pyrazol-4-yl)-but-2-enyliden)-5-methyl-2-(4-sulfophenyl)-2,4-dihydro-pyrazol-3-one (8a) 
Tetrasodium 4-(3-(3-Carboxy-5-oxo-1-(4-sulfophenyl)-1,5-dihydropyrazol-4-yliden)-propenyl)-5-hydroxy-1-(4-sulfophenyl)-1H-pyrazol-3-carboxylic acid (9a) 
Dipotassium 4-(5-(5-Hydroxy-3-methyl-1-(4-sulfophenyl)-1H-pyrazol-4-yl)-penta-2,4-dienyliden)-5-methyl-2-(4-sulfophenyl)-2,4-dihydropyrazol-3-one (14a) 
Dipotassium 4-(5-(3-carboxy-5-oxo-1-(4-sulfo-phenyl)-1,5-dihydro-pyrazol-4-yliden)-penta-1,3-dienyl)-5-hydroxy-1-(4-sulfo-phenyl)-1H-pyrazol-3-carboxylic acid (15a) 
Triethylammonium-5-(3-(5-cyano-1-ethyl-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydro-pyridin-3-carbonitrile (24a) 
Ammonium 5-(3-(5-cyano-1-ethyl-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydro-pyridin-3-carbonitrile (24b)
The total amount of dyes of formula (Ia)(Ib) or (II) to (IV) in the colorants according to the invention for coloring keratin dyes is from 0.01 to 5 wt % and preferably from 0.5 to 4 wt %.
The colorants according to the invention also contain at least one natural or synthetic nonoxidative dye. Suitable synthetic nonoxidative dyes are, for example, the nitro, azo, triphenylmethane, quinone, anthraquinone or acid dyes, particularly
1,4-bis-[(2-hydroxyethyl)amino]-2-nitrobenzene, 1-(2-hydroxyethyl)amino-2-nitro-4-[di(2-hydroxyethyl)amino]benzene (HC Blue No. 2), 1-amino-3-methyl-4-[(hydroxyethyl)amino-6-nitrobenzene (HC Violet No. 1), 4-[ethyl-(2-hydroxyethyl)amino]-1-[(2-hydroxyethyl)amino]-2-nitrobenzene hydrochloride (HC Blue No. 12), 4-[di(2-hydroxyethyl)amino]-1-[(2-methoxyethyl)amino-2-nitrobenzene (HC Blue No. 11), 1-[2,3-dihydroxypropyl)amino-4-[methyl-2-(2-hydroxyethyl)amino]-2-nitrobenzene (HC Blue No. 10), 1-[(2,3-dihydroxypropyl)amino]-4-[ethyl-(2-hydroxyethyl)amino]-2-nitrobenzene hydrochloride (HC Blue No. 9), 1-(3-hydroxypropylamino)-4-[di(2-hydroxyethyl)amino]-2-nitrobenzene (HC Violet No. 2), 1-methylamino-4-[methyl-(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC Blue No. 6), 2-[(4-amino-2-nitrophenyl)amino]-5-dimethylaminobenzoic acid (HC Blue No. 13), 1-amino-4-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Red No. 7), 2-amino-4,6-dinitrophenol, 4-amino-2-nitrodiphenylamine (HC Red No. 1), 1-amino-4-[di(2-hydroxyethyl)amino]-2-nitrobenzene hydrochloride (HC Red No. 13), 1-amino-5-chloro-4-[(2-hydroxyethyl)amino]-2-nitrobenzene, 4-amino-1-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Red No. 3), 4-amino-3-nitrophenol, 4-[(2-hydroxyethyl)amino-3-nitrophenol, 1-[(2-aminoethyl)amino]-4-(2-hydroxyethoxy)-2-nitrobenzene (HC Orange No. 2), 4-(2,3-dihydroxypropoxy)-1-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Orange No. 3), 1-amino-5-chloro-4-[(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC Red No. 10), 5-chloro-1,4-[di(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC Red No. 11), 2-[(2-hydroxyethyl)amino]-4,6-dinitrophenol, 4-ethylamino-3-nitrobenzoic acid, 2-[(4-amino-2-nitrophenyl)amino]benzoic acid, 2-chloro-6-ethylamino-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol hydrochloride, 4-[(3-hydroxypropyl)amino]-3-nitrophenol, 2,5-diamino-6-nitropyridine, 1,2,3,4-tetrahydro-6-nitroquinoxaline, 7-amino-3,4-dihydro-6-nitro-2H-1,4-benzoxazine (HC Red No. 14), 1-amino-2-[(2-hydroxyethyl)amino]-5-nitrobenzene (HC Yellow No. 5), 1-(2-hydroxyethoxy)-2-[(2-hydroxyethyl)amino]-5-nitrobenzene (HC Yellow No. 4), 1-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Yellow No. 2), 2-[(hydroxyethyl)amino]-1-methoxy-5-nitrobenzene, 2-amino-3-nitrophenol, 1-(2-hydroxyethoxy)-3-methylamino-4-nitrobenzene, 2,3-(dihydroxpropoxy)-3-methylamino-4-nitrobenzene, 2-[(2-hydroxyethyl)amino]-5-nitrophenol (HC Yellow No. 11), 3-[(2-aminoethyl)amino]-1-methoxy-4-nitrobenzene hydrochloride (HC Yellow No. 9), 1-[(2-ureidoethyl)amino]-4-nitrobenzene, 4-[(2,3-dihydroxypropyl)amino]-3-nitro-1-trifluoromethylbenzene (HC Yellow No. 6), 1-chloro-2,4-bis-[(2-hydroxyethyl)amino]-5-nitrobenzene (HC Yellow No. 10), 4-[(2-hydroxyethyl)amino]-3-nitro-1-methylbenzene, 1-chloro-4-[(2-hydroxyethyl)-amino-3-nitrobenzene (HC Yellow No. 12), 4-[(2-hydroxyethyl)amino-3-nitro-1-trifluoromethylbenzene (HC Yellow No. 13), 4-[(2-hydroxyethyl)amino]-3-nitrobenzonitrile (HC Yellow No. 14), 4-[(2-hydroxyethyl)amino]-3-nitrobenzamide (HC Yellow No. 15, 1,4-di[(2,3-dihydroxypropyl)amino]-9,10-anthraquinone, 1-[(2-hydroxyethyl)amino]-4-methylamino-9,10-anthraquinone (C.I. 61505, Disperse Blue No. 3), 2-[(2-aminoethyl)amino]-9,10-anthraquinone (HC Orange No. 5), 1-hydroxy-4-[(4-methyl-2-sulfophenyl)amino]-9,10-anthraquinone, 1-[(3-aminopropyl)amino]-4-methylamino-9,10-anthraquinone (HC Blue No. 8), 1-[(3-aminopropyl)amino]-9,10-anthraquinone (HC Red No. 8), 1,4-diamino-2-methoxy-9,10-anthraquinone (C.I. 62015, Disperse Red No. 11, Solvent Violet No. 26), 1,4-dihydroxy-5,8-bis-[(2-hydroxyethyl)amino]-9,10-anthraquinone (C.I. 62500, Disperse Blue No. 7, Solvent Blue No. 69), 1-[(di(2-hydroxyethyl)amino]-3-methyl-4-[(4-nitrophenyl)azo]benzene (C.I. 11210, Disperse Red No. 17), 4-[(4-aminophenyl)azo]-1-[di(2-hydroxyethyl)amino]-3-methylbenzene (HC Yellow No. 7), 2,6-diamino-3-[(pyridin-3-yl)azo)pyridine, 6-hydroxy-5-[(4-sulfophenyl)azo]-2-naphthalenesulfonic acid disodium salt (C.I. 15985; Food Yellow No. 3; FDandC Yellow No. 6), 2,4-dinitro-1-naphthol-7-sulfonic acid disodium salt (C.I. 10316; Acid Yellow No. 1); Food Yellow No. 1), 2-(indan-1,3-dione-2-yl)quinoline-x,x-sulfonic acid (mixture of mono and disulfonic acid) (C.I. 47005; DandC Yellow No. 5; Food Yellow No. 13); Acid Yellow No. 3), 5-hydroxy-1-(4-sulfophenyl)-[(4-[(4-sulfophenyl)azo]pyrazole-3-carboxylic acid trisodium salt (C.I. 19140; Food Yellow No. 4; Acid Yellow No. 23), 9-(2-carboxyphenyl)-6-hydroxy-3H-xanthen-3-one (C.I. 45350; Acid Yellow No. 73; DandC Yellow No. 8), 5-[(2,4-dinitrophenyl)amino]-2-phenylaminobenzenesulfonic acid sodium salt (C.I. 10385; Acid Orange No. 3), 4-[(2,4-dihydroxyphenyl)axo]benzenesulfonic acid monosodium salt (C.I. 14270; Acid Orange No. 6), 4-[(2-hydroxy-1-naphthyl)azo)benzenesulfonic acid sodium salt (C.I. 15510; Acid Orange No. 7), 4-[(2,4-dihydroxy-3-[(2,4-dimethylphenyl)azo]phenyl)azo]benzenesulfonic acid sodium salt (C.I. 20170; Acid Orange No. 24), 4-hydroxy-3-[(4-sulfo-1-naphthyl)azo]-1-naphthalenesulfonic acid disodium salt (C.I. 14720; Acid Red No. 14), 6-hydroxy-5-[(4-sulfo-1-naphthyl)azo-2,4-naphthalenedisulfonic acid trisodium salt (C.I. 16255; Ponceau 4R; Acid Red No. 18), 3-hydroxy-4-[(4-sulfo-1-naphthyl)azo]-2,7-naphthalenedisulfonic acid trisodium salt (C.I. 16185; Acid Red No. 27), 8-amino-1-hydroxy-2-(phenylaxo)-3,6-naphthalenedisulfonic acid disodium salt (C.I. 17200; Acid Red No. 33), 5-(acetylamino)-4-hydroxy-3-[(2-methylphenyl)azo]-2,7-naphthalenedisulfonic acid disodium salt (C.I. 18065; Acid Red No.35), 2-(3-hydroxy-2,4,5,7-tetraiododibenzopyran-6-one-9-yl)benzoic acid disodium salt (C.I. 45430; Acid Red No. 51), N-[6-(diethylamino)-9-(2,4-disulfophenyl)-3H-xanthen-3-ylidene-N-ethylethaneammonium hydroxide, inner salt, sodium salt (C.I. 45100; Acid Red No. 52), 8-[(4-(phenyl-azo) phenyl)azo]-7-naphthol-1,3-disulfonic acid disodium salt (C.I. 27290; Acid Red No. 73), 2xe2x80x2,4xe2x80x2,5xe2x80x2,7xe2x80x2-tetrabromo-3xe2x80x2,6xe2x80x2-dihydroxyspiro[isobenzofuran-1(3H),-9xe2x80x2[9H]xanthene-3-one disodium salt (C.I. 45380; Acid Red No. 87), 2xe2x80x2,4xe2x80x2,5xe2x80x2,7xe2x80x2-tetrabromo-4,5,6,7-tetrachloro-3xe2x80x2, 6xe2x80x2-dihydroxyspiro[isobenzofuran 1(3H),9xe2x80x2[9H]xanthene]-3-one disodium salt (C.I. 45410; Acid Red No. 92), 3xe2x80x2,6xe2x80x2-dihydroxy-4xe2x80x2,5xe2x80x2-diiodospiro[isobenzofuran-1(3H),9xe2x80x2(9H)-xanthene]-3-one disodium salt (C.I. 45425; Acid Red No.95), (2-sulfophenyl)-di-[4-(ethyl((4-sulfophenyl) methyl)-amino) phenyl]carbenium disodium salt, betaine (C.I. 42090; Acid Blue No. 9; FDandC Blue No. 1), 1,4-bis-[(2-sulfo-4-methylphenyl)amino]-9,10-anthraquinone disodium salt (C.I. 61570; Acid Green No. 25), bis-[4-dimethylamino)phenyl]-(3,7-disulfo-2-hydroxy-1-naphthyl)carbenium inner salt, monosodium salt (C.I. 44090; Food Green No. 4; Acid Green No. 50), bis-[4-(diethylamino)phenyl]-(2,4-disulfophenyl)carbenium inner salt, sodium salt (2:1) (C.I. 42045; Food Blue No. 3; Acid Blue No. 1), bis-[4-(diethylamino)phenyl](5-hydroxy-2,4-disulfophenyl)carbenium inner salt, calcium salt (2:1) (C.I. 42051; Acid Blue No. 3), 1-amino-4-(cyclohexylamino)-9,10-anthraquinone-2-sulfonic acid sodium salt (C.I. 62045; Acid Blue No. 62), 2-(1,3-dihydro-3-oxo-5-sulfo-2H-indol-2-ylidene)-2,3-dihydro-3-oxo-1H-indol-5-sulfonic acid disodium salt (C.I. 73015; Acid Blue No. 74), 9-(2-carboxy-phenyl)-3-[(2-methylphenyl)amino]-6-[(2-methyl-4-sulfophenyl)amino]xanthylium inner salt, monosodium salt (C.I. 45190; Acid Violet No.9), 1-hydroxy-4-[(4-methyl-2-sulfophenyl)amino]-9,10-anthraquinone sodium salt (C.I. 60730; DandC Violet No.2; Acid Violet No. 43), bis-[3-nitro-4-[(4-phenylamino)-3-sulfophenylamino]phenyl]sulfone (C.I. 10410; Acid Brown No. 13), 5-amino-4-hydroxy-6-[(4-nitrophenyl)azo]-3-(phenylazo)-2,7-naphthalenedisulfonic acid disodium salt (C.I. 20470; Acid Black No. 1), 3-hydroxy-4-[(2-hydroxy-1-naphthyl)azo-7-nitro-1-naphthalenesulfonic acid chromium complex (3:2) (C.I. 15711; Acid Black No.52), 3-[(2,4-dimethyl-5-sulfophenyl)azo]-4-hydroxy-1-naphthalenesulfonic acid disodium salt (C.I. 14700; Food Red No. 1; Ponceau SX; FDandC Red No. 4), 4-(acetylamino)-5-hydroxy-6-[(7-sulfo-4-[(4-sulfophenyl)azo]-1-naphthyl)azo]-1,7-naphthalenedisulfonic acid tetrasodium salt (C.I. 28440; Food Black No.1) and 3-hydroxy-4-(3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-ylazo)naphthalene-1-sulfonic acid sodium salt chromium complex (Acid Red No. 195).
Although the polymethine dyes contained in the colorant according to the invention are by definition anionic in nature, some of these dyes, particularly monomethine oxonols (1) and (2) are, surprisingly, fully compatible with cationic (xe2x80x9cbasicxe2x80x9d) dyes, for example 9-(dimethylamino)benzo[a]phenoxazin-7-ium chloride (C.I. 51175; Basic Blue No. 6), di[4-diethylamino)phenyl][4-(ethylamino)naphthyl]-carbenium chloride (C.I. 42595; Basic Blue No. 7), 3,7-di(dimethylamino)phenothiazin-5-ium chloride, (C.I. 52015; Basic Blue No. 9), di[4-(dimethylamino)phenyl][4-(phenylamino)naphthyl]carbenium chloride (C.I. 44045); Basic Blue 26), 2-[4-(ethyl(2-hydroxyethyl)amino)phenyl)axo]-6methoxyoxy-3-methylbenzothiazolium methylsulfate (C.I. 11154; Basic Blue 41), 8-amino-2-bromo-5-hydroxy-4-imino-6-[(3-(trimethylammonio)phenyl)amino]-1(4H)-naphthalenone chloride (C.I. 56059; Basic Blue No. 99), bis[4-(dimethylamino)phenyl][4-(methylamino)phenyl]carbenium chloride (C.I. 42535, Basic Violet No. 1), tris-[4-(dimethylamino)phenyl]carbenium chloride (C.I. 42555; Basic Violet No. 3), 2-[3,6-diethylamino)dibenzopyranium-9-yl benzoic acid chloride (C.I. 45170; Basic Violet No. 10), di(4-aminophenyl)-(4-amino-3-methylphenyl)carbenium chloride (C.I. 42510; Basic Violet No. 14), 1,3-bis[(2,4-diamino-5-methylphenyl)azo]-3-methylbenzene (C.I. 21010, Basic Brown No. 4), 1-[(4-aminophenyl)azo-7-(trimethylammonio)-2-naphthol chloride (C.I. 12250, Basic Brown No. 16), 1-[(4-aminophenyl)azo-7-(trimethylammonio)-2-naphthol chloride (C.I. 12250, Basic Brown No. 16), 1-[(4-amino-2-nitrophenyl)azo]-7-(trimethylammonio)-2-naphthol chloride (Basic Brown No. 17),1-[(4-amino-3-nitrophenyl)azo]-7-(trimethylammonio)-2-naphthol chloride (C.I. 12251; Basic Brown No. 17) [sicxe2x80x94Translator], 3,7-diamino-2,8-dimethyl-5-phenylphenazinium chloride (C.I. 50240; Basic Red No. 2), 1,4-dimethyl-5-[(4-(dimethylamino)phenyl)azo]-1,2,4-triazolium chloride (C.I. 11055; Basic Red No. 22), 2-hydroxy-1[(2-methoxyphenyl)azo-7-(trimethylammonio)naphthalene chloride (C.I. 12245; Basic Red No. 76), 2-[2-(2,4-dimethoxyphenyl)amino)ethenyl]-1,3,3-trimethyl-3H-indol-1-ium chloride (C.I. 48055; Basic Yellow No. 11), 3-methyl-1-phenyl-4-[(3-(trimethylammonio)phenyl)azo]pyrazol-5-one chloride (C.I. 12719; Basic Yellow No. 57) or bis-[4-(diethylamino)phenyl]phenylcarbenium hydrogen sulfate (1:1) (C.I. 42040; Basic Green No: 1).
The total amount of natural or synthetic nonoxidative dyes contained in the colorant according to the invention is from 0.01 to 15 wt % and particularly from 0.1 to 12 wt %.
To increase the color intensity, conventional carriers used in cosmetic systems can be employed. Suitable compounds are, for example, benzyl alcohol, furfuryl alcohol, 2-hydroxymethylthiophene, vanillin or isovanillin. Other suitable carriers are described in German Unexamined Patent Application DE 196 18 595, the disclosures of which are hereby incorporated by reference.
The colorants according to the invention for tinting keratin fibers can be used in the form of, for example, a solution, particularly an aqueous-alcoholic solution, or a cream, gel or emulsion. Suitable solvents besides water are, for example the lower aliphatic monohydric or polyhydric alcohols, the esters and ethers thereof or mixtures of said solvents with each other or with water. The maximum boiling point of the aforesaid suitable solvents is about 400xc2x0 C., a boiling point from 20xc2x0 C. to 250xc2x0 C. being preferred.
It is also possible to dispense said colorants by means of an atomizer or some other suitable pumping or spraying device or, in admixture with conventional propellants liquefied under pressure, dispense them from a pressurized container in the form of an aerosol spray or aerosol foam.
The pH of the colorants according to the invention is from 2 to 11, a pH from 2.5 to 8 being particularly preferred. An alkaline pH is preferably obtained with ammonia, but an organic amine, for example monoethanolamine or triethanolamine, can be used in place of ammonia. To obtain an acidic pH, on the other hand, an organic or inorganic acid, for example hydrochloric, sulfuric, phosphoric, ascorbic, glycolic or lactic acid, can be used.
Naturally, the aforedescribed colorants can optionally contain other common additives suitable for keratin fiber colorants, for example hair-care agents, wetting agents, thickeners, softeners, preservatives and perfumes as well as other additives listed in the following.
The colorants according to the invention can also contain wetting agents or emulsifiers from the classes of anionic, amphoteric, nonionic or zwitterionic surface-active agents, such as fatty alcohol sulfates, alkanesulfonates, alkylbenzenesulfonates, alkylbetaines, xcex1-olefinsulfonates, ethoxylated fatty alcohols, ethoxylated nonylphenols, fatty alkanolamines, ethoxylated fatty esters, fatty alcohol polyglycol ether sulfates, alkyl polyglucosides, thickeners such as the higher fatty alcohols, starch, alginates, bentonites, cellulose derivatives, vaseline, paraffin oil and fatty acids, water-soluble polymeric thickeners such as various types of natural gum, guar gum, xanthan gum, carob bean flour, pectin, dextran, agar, amylose, amylopectin, dextrins, clays, or fully synthetic hydrocolloids, such as polyvinyl alcohol, furthermore hair-care agents such as lanolin derivatives, cholesterol, pantothenic acid, water-soluble polymers, protein derivatives, provitamins, vitamins, plant extracts, sugar and betaine, auxiliary agents such as humectants, electrolytes, antioxidants, fatty amides, sequestrants, film-forming agents and preservatives.
The aforedescribed colorants can also contain natural or synthetic polymers or modified natural polymers whereby the keratin fiber is strengthened while it is being colored. Such agents are generally referred to as shade or color enhancers. Suitable among the synthetic polymers known to be used in cosmetics for this purpose are, for example, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, or polyacrylic compounds, such as polyacrylic acid or polymethacrylic acid, polyacrylonitrile, polyvinyl acetates and copolymers of such compounds, for example polyvinylpyrrolidone-vinyl acetate copolymers. Suitable natural or modified natural polymers are, for example, chitosan, (deacetylated chitin) or chitosan derivatives.
The said constituents are used in amounts that are normal for such purposes. For example, the wetting agents and emulsifiers are used in an amount of about 0.5 to 30 wt %, the thickeners in an amount from about 0.1 to 25 wt % and the hair-care agents in an amount from about 0.1 to 5 wt %. The aforesaid polymers can be used in the colorants of the invention in amounts that are normal for such colorants, particularly in an amount from about 1 to 5 wt %.
The keratin fiber colorants of the invention are particularly well suited for the coloring of hair. For this purpose, the colorants of the invention are applied to the hair in the usual manner in an amount sufficient for hair coloring and, in general, in an amount from about 50 to 150 grams. After an exposure time sufficient for hair coloring, usually about 10 to 45 min at 20xc2x0 to 50xc2x0 C. and preferably 15 to 30 min at about 40xc2x0 C., the hair is rinsed with water, optionally washed with a shampoo and/or an aqueous solution of a weak organic acid, for example citric or tartaric acid, again rinsed and then dried.
The colorants with the additional strengthening action are used in the known and conventional manner by wetting the hair with them, styling the hair and then drying.
As regards the range of possible coloring, the hair colorants according to the invention can give rise to a broad spectrum of different shades ranging from natural colors to highly fashionable bright shades, depending on the type and composition of the dyes used. The advantageous properties of the novel colorants manifest themselves particularly on light-damaged and weather-damaged or permanently waved hair. In particular, the resulting tints are characterized by very good stability and wash-out resistance.
The monomethine oxonol dyes (m=n=0) can be prepared from the corresponding heterocyclic compounds and trialkyl orthoesters or formamides as bridge precursors. Numerous compounds are described by B. Schied, J. prak. Chem 157, page 203 ff (1941) and by S. Hxc3xcnig, Annalen 574, page 106 ff (1951) as well in the literature cited therein. According to German Unexamined Patent Application DE 20 12 050, the trimethine oxonols (m+n=1) can be prepared from tetramethoxypropane, trimethoxypropene or malonaldehyde dianil. The pentamethine oxonols (m+n=2) can be prepared from N-acceptor-substituted pyridinium salts by opening the pyridine ring (xe2x80x9cZincke cleavagexe2x80x9d) or from an appropriate derivative, for example glutaconaldehyde dianil. A complete review of this subject can be found in Houben-Weyl 7/1, 4th edition (1954) on pages 263 ff and in the literature cited therein.